Microbiocidal phenylamidine derivatives

ABSTRACT

Compounds of the formula (I) wherein the subsitiuents are as defined in claim  1.  Furthermore, the present invention relates to agrochemical compositions which comprise compounds of formula (I), to preparation of these compositions, and to the use of the compounds or compositions in agriculture or horticulture for combating, preventing or controlling infestation of plants, harvested food crops, seeds or non-living materials by phytopathogenic microorganisms, in particular fungi.

The present invention relates to microbiocidal phenylamidinederivatives, e.g. as active ingredients, which have microbiocidalactivity, in particular fungicidal activity. The invention also relatesto preparation of these phenylamidine derivatives, to intermediatesuseful in the preparation of these phenylamidine derivatives, to thepreparation of these intermediates, to agrochemical compositions whichcomprise at least one of the phenylamidine derivatives, to preparationof these compositions and to the use of the phenylamidine derivatives orcompositions in agriculture or horticulture for controlling orpreventing infestation of plants, harvested food crops, seeds ornon-living materials by phytopathogenic microorganisms, in particularfungi.

Certain fungicidal phenylamidine compounds are described in WO2000/046184.

It has now surprisingly been found that certain novel phenylamidinederivatives have favourable fungicidal properties.

The present invention therefore provides compounds of formula (I)

wherein

R¹ and R² are each independently selected from C₁-C₄alkyl andC₃-C₈cycloalkyl; or

R¹ and R² together with the nitrogen atom to which they are attachedform a three- to six-membered saturated cyclic group;

R³ is hydrogen, halogen or C₁-C₄ alkyl;

R⁴ and R⁵ are each independently selected from hydrogen and C₁-C₄ alkyl;or

R⁴ and R⁵ together with the carbon atom to which they are attached forma carbonyl 25 group (C═O);

X is O, S or NCH₃;

n is O or 1;

and salts, metal complexes, stereoisomers and N-oxides thereof.

In a second aspect the present invention provides an agrochemicalcomposition comprising a compound of formula (I).

Compounds of formula (I) may be used to control phytopathogenicmicroorganisms. Thus, in order to control a phytopathogen a compound offormula (I), or a composition comprising a compound of formula (I),according to the invention may be applied directly to the phytopathogen,or to the locus of a phytopathogen, in particular to a plant susceptibleto attack by phytopathogens.

Thus, in a third aspect the present invention provides the use of acompound of formula (I), or a composition comprising a compound offormula (I), as described herein to control a phytopathogen.

In a further aspect the present invention provides a method ofcontrolling phytopathogens, comprising applying a compound of formula(I), or a composition comprising a compound of formula (I), as describedherein to said phytopathogen, or to the locus of said phytopathogen, inparticular to a plant susceptible to attack by a phytopathogen.

Compounds of formula (I) are particularly effective in the control ofphytopathogenic fungi.

Thus, in a yet further aspect the present invention provides the use ofa compound of formula (I), or a composition comprising a compound offormula (I), as described herein to control phytopathogenic fungi.

In a further aspect the present invention provides a method ofcontrolling phytopathogenic fungi, comprising applying a compound offormula (I), or a composition comprising a compound of formula (I), asdescribed herein to said phytopathogenic fungi, or to the locus of saidphytopathogenic fungi, in particular to a plant susceptible to attack byphytopathogenic fungi.

Where substituents are indicated as being optionally substituted, thismeans that they may or may not carry one or more identical or differentsubstituents, e.g. one to four substituents. Normally not more thanthree such optional substituents are present at the same time.Preferably not more than two such optional substituents are present atthe same time (i.e. the group may be optionally substituted by one ortwo of the substituents indicated as “optional”). Where the “optionalsubstituent” group is a larger group, such as cycloalkyl or phenyl, itis most preferred that only one such optional substituent is present.Where a group is indicated as being substituted, e.g. alkyl, thisincludes those groups that are part of other groups, e.g. the alkyl inalkylthio.

The term “halogen” refers to fluorine, chlorine, bromine or iodine,preferably fluorine, chlorine or bromine.

Alkyl substituents (either alone or as part of a larger group, such asalkoxy-, alkylthio-) may be straight-chained or branched. Alkyl on itsown or as part of another substituent is, depending upon the number ofcarbon atoms mentioned, for example, methyl, ethyl, n-propyl, n-butyl,n-pentyl, n-hexyl and the isomers thereof, for example, iso-propyl,iso-butyl, sec-butyl, tert-butyl or iso-amyl.

Cycloalkyl substituents may be saturated or partially unsaturated,preferably fully saturated, and are, for example, cyclopropyl,cyclobutyl, cyclopentyl or cyclohexyl.

Haloalkyl groups (either alone or as part of a larger group, eg.haloalkyloxy) may contain one or more identical or different halogenatoms and, for example, may stand for CH₂Cl, CHCl₂, CCl₃, CH₂F, CHF₂,CF₃, CF₃CH₂, CH₃CF₂, CF₃CF₂ or CCl₃CCl₂.

Alkoxy means a radical —OR, where R is alkyl, e.g. as defined above.Alkoxy groups include, but are not limited to, methoxy, ethoxy,1-methylethoxy, propoxy, butoxy, 1-methylpropoxy and 2-methylpropoxy.

The presence of one or more possible asymmetric carbon atoms in acompound of formula (I) means that the compounds may occur in opticallyisomeric forms, i.e. enantiomeric or diastereomeric forms. Alsoatropisomers may occur as a result of restricted rotation about a singlebond. Formula (I) is intended to include all those possible isomericforms and mixtures thereof. The present invention includes all thosepossible isomeric forms and mixtures thereof for a compound of formula(I). Likewise, formula (I) is intended to include all possibletautomers. The present invention includes all possible tautomeric formsfor a compound of formula (I).

In each case, the compounds of formula (I) according to the inventionare in free form, in oxidized form as a N-oxide or in salt form, e.g. anagronomically usable salt form.

N-oxides are oxidized forms of tertiary amines or oxidized forms ofnitrogen containing heteroaromatic compounds. They are described forinstance in the book “Heterocyclic N-oxides” by A. Albini and S. Pietra,CRC Press, Boca Raton 1991.

Preferred values of R¹, R², R³, R⁴, R⁵, X and n are, in any combinationthereof, as set out below:

Preferably R¹ and R² are each independently C₁-C₄ alkyl.

More preferably R¹ and R² are each independently selected from methyl,ethyl and isopropyl.

Even more preferably R¹ is methyl, ethyl or isopropyl and R² is methylor ethyl.

Most preferably R¹ is ethyl or isopropyl and R² is methyl.

Preferably R³ is halogen or C₁-C₃ alkyl.

More preferably R³ is fluoro, chloro or methyl.

Even more preferably R³ is chloro or methyl.

Most preferably R³ is methyl.

Preferably R⁴ and R⁵ are each independently selected from hydrogen andmethyl, or R⁴ and R⁵ together with the carbon atom to which they areattached form a carbonyl group.

More preferably R⁴ and R⁵ are both hydrogen, or R⁴ and R⁵ together withthe carbon atom to which they are attached form a carbonyl group.

Most preferably R⁴ and R⁵ are both hydrogen.

Preferably X is O or S.

Most preferably X is O.

Most preferably n is 1.

Embodiments according to the invention are provided as set out below.

Embodiment 1 provides compounds of formula (I), or a salt, stereoisomeror N-oxide thereof, as defined above.

Embodiment 2 provides compounds according to embodiment 1, or a salt,stereoisomer or N-oxide thereof, wherein R¹ and R² are eachindependently C₁-C₄ alkyl.

Embodiment 3 provides compounds according to embodiment 1 or 2, or asalt, stereoisomer or N-oxide thereof, wherein R³ is halogen or C₁-C₃alkyl.

Embodiment 4 provides compounds according to any one of embodiments 1, 2or 3, or a salt, stereoisomer or N-oxide thereof, wherein R⁴ and R⁵ areeach independently selected from hydrogen and methyl, or R⁴ and R⁵together with the carbon atom to which they are attached form a carbonylgroup.

Embodiment 5 provides compounds according to any one of embodiments 1,2, 3 or 4, or a salt, stereoisomer or N-oxide thereof, wherein X is O orS.

Embodiment 6 provides compounds according to any one of embodiments 1,2, 3, 4, or 5, or a salt, stereoisomer or N-oxide thereof, wherein R¹and R² are each independently selected from methyl, ethyl and isopropyl.

Embodiment 7 provides compounds according to any one of embodiments 1,2, 3, 4, 5, or 6, or a salt, stereoisomer or N-oxide thereof, wherein R³is fluoro, chloro or methyl. Embodiment 8 provides compounds accordingto any one of embodiments 1, 2, 3, 4, 5, 6, or 7, or a salt,stereoisomer or N-oxide thereof, wherein R⁴ and R⁵ are both hydrogen, orR⁴ and R⁵ together with the carbon atom to which they are attached forma carbonyl group.

Embodiment 9 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, or 8, or a salt, stereoisomer or N-oxide thereof,wherein R¹ is methyl, ethyl or isopropyl and R² is methyl or ethyl.

Embodiment 10 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, or 9, or a salt, stereoisomer or N-oxide thereof,wherein R³ is chloro or methyl.

Embodiment 11 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9 or 10, or a salt, stereoisomer or N-oxidethereof, wherein R¹ is ethyl or isopropyl and R² is methyl.

Embodiment 12 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10 or 11, or a salt, stereoisomer or N-oxidethereof, wherein R³ is methyl.

Embodiment 13 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, or a salt, stereoisomer or N-oxidethereof, wherein R⁴ and R⁵ are both hydrogen.

Embodiment 14 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12 or 13, or a salt, stereoisomer orN-oxide thereof, wherein n is 1.

Embodiment 15 provides compounds according to any one of embodiments 1,2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a salt, stereoisomer orN-oxide thereof, wherein X is O.

A preferred group of compounds according to the invention are those offormula (I-1) which are compounds of formula (I) wherein

R¹ and R² are each independently C₁-C₄ alkyl;

R³ is halogen or C₁-C₃ alkyl;

R⁴ and R⁵ are each independently selected from hydrogen and methyl, orR⁴ and R⁵ together with the carbon atom to which they are attached forma carbonyl group;

X is O, S or NCH₃;

n is O or 1;

or a salt, stereoisomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-1a) which are compounds of formula (I-1) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-1b) which are compounds of formula (I-1) wherein X is S.

Another group of compounds according to this embodiment are compounds offormula (I-1c) which are compounds of formula (I-1) wherein X is NCH₃.

A further preferred group of compounds according to the invention arethose of formula (I-2) which are compounds of formula (I) wherein

R¹ and R² are each independently selected from methyl, ethyl andisopropyl;

R³ is fluoro, chloro or methyl;

R⁴ and R⁵ are both hydrogen, or R⁴ and R⁵ together with the carbon atomto which they are attached form a carbonyl group;

X is O, S or NCH₃;

n is 0 or 1;

or a salt, stereoisomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-2a) which are compounds of formula (I-2) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-2b) which are compounds of formula (I-2) wherein X is S.

Another group of compounds according to this embodiment are compounds offormula (I-2c) which are compounds of formula (I-2) wherein X is NCH₃.

A further preferred group of compounds according to the invention arethose of formula (I-3) which are compounds of formula (I) wherein

R¹ is methyl, ethyl or isopropyl and R² is methyl or ethyl;

R³ is chloro or methyl;

R⁴ and R⁵ are both hydrogen, or R⁴ and R⁵ together with the carbon atomto which they are attached form a carbonyl group;

X is O, S or NCH₃;

n is O or 1;

or a salt, stereoisomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-3a) which are compounds of formula (I-3) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-3b) which are compounds of formula (I-3) wherein X is S.

Another group of compounds according to this embodiment are compounds offormula (I-3c) which are compounds of formula (I-3) wherein X is NCH₃.

A further preferred group of compounds according to the invention arethose of formula (I-4) which are compounds of formula (I) wherein

R¹ is ethyl or isopropyl and R² is methyl;

R³ is methyl;

R⁴ and R⁵ are both hydrogen;

X is O or S;

n is 0 or 1 (preferably n is 1);

or a salt, stereoisomer or N-oxide thereof.

One group of compounds according to this embodiment are compounds offormula (I-4a) which are compounds of formula (I-4) wherein X is O.

Another group of compounds according to this embodiment are compounds offormula (I-4b) which are compounds of formula (I-4) wherein X is S.

Certain preferred compounds of formula (I) are:

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine

N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-isopropyl-N-methyl-formamidine

N′-[2-chloro-5-hydroxy-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-ethyl-N-methyl-formamidine

N-ethyl-N′-[5-hydroxy-2-methyl-4-[4-oxo-2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrothiophen-2-yl]phenyl]-N-methyl-formamidine

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine

Compounds according to the invention may possess any number of benefitsincluding, inter alia, advantageous levels of biological activity forprotecting plants against diseases that are caused by fungi or superiorproperties for use as agrochemical active ingredients (for example,greater biological activity, an advantageous spectrum of activity, anincreased safety profile, improved physico-chemical properties, orincreased biodegradability).

Specific examples of compounds of formula (I) are illustrated in theTables 1 to 4 below.

Each of Tables 1 to 4, which follow Table P below, make available 48compounds of the formula (I-A)

wherein R², R³, X and n are as defined in Table P (below) and R⁴ and R⁵are as defined in Tables 1 to 4, respectively.

Thus, Table 1 individualizes 48 compounds of formula (I-A) wherein foreach row of Table P, R⁴ and R⁵ are as defined in Table 1; similarly,Table 2 individualizes 48 compounds of formula (I-A) wherein for eachrow of Table P, R⁴ and R⁵ are as defined in Table 2; and so on forTables 3 and 4.

TABLE P Entry R² R³ X n P.01 Me H O 0 P.02 Me H O 1 P.03 Me H S 0 P.04Me H S 1 P.05 Me Cl O 0 P.06 Me Cl O 1 P.07 Me Cl S 0 P.08 Me Cl S 1P.09 Me Me O 0 P.10 Me Me O 1 P.11 Me Me S 0 P.12 Me Me S 1 P.13 Et H O0 P.14 Et H O 1 P.15 Et H S 0 P.16 Et H S 1 P.17 Et Cl O 0 P.18 Et Cl O1 P.19 Et Cl S 0 P.20 Et Cl S 1 P.21 Et Me O 0 P.22 Et Me O 1 P.23 Et MeS 0 P.24 Et Me S 1 P.25 i-Pr H O 0 P.26 i-Pr H O 1 P.27 i-Pr H S 0 P.28i-Pr H S 1 P.29 i-Pr Cl O 0 P.30 i-Pr Cl O 1 P.31 i-Pr Cl S 0 P.32 i-PrCl S 1 P.33 i-Pr Me O 0 P.34 i-Pr Me O 1 P.35 i-Pr Me S 0 P.36 i-Pr Me S1 P.37 cyclopropyl H O 0 P.38 cyclopropyl H O 1 P.39 cyclopropyl H S 0P.40 cyclopropyl H S 1 P.41 cyclopropyl Cl O 0 P.42 cyclopropyl Cl O 1P.43 cyclopropyl Cl S 0 P.44 cyclopropyl Cl S 1 P.45 cyclopropyl Me O 0P.46 cyclopropyl Me O 1 P.47 cyclopropyl Me S 0 P.48 cyclopropyl Me S 1

Table 1: This table discloses 48 compounds 1.01 to 1.48 of the formulaI-A wherein R⁴ and R⁵ are both hydrogen, and wherein the variables R²,R³, X and n have the specific meaning given in the corresponding line ofTable P. For example, compound 1.01 has the following structure:

Table 2: This table discloses 48 compounds 2.01 to 2.48 of the formulaI-A wherein R⁴ and R⁵ are both methyl, and wherein the variables R², R³,X and n have the specific meaning given in the corresponding line ofTable P.

Table 3: This table discloses 48 compounds 3.01 to 3.48 of the formulaI-A wherein R⁴ and R⁵ are both ethyl, and wherein the variables R², R³,X and n have the specific meaning given in the corresponding line ofTable P.

Table 4: This table discloses 48 compounds 4.01 to 4.48 of the formulaI-A wherein R⁴ and R⁵ together form a carbonyl group, and wherein thevariables R², R³, X and n have the specific meaning given in thecorresponding line of Table P.

Compounds of the present invention can be made as shown in the followingschemes, in which, unless otherwise stated, the definition of eachvariable is as defined above for a compound of formula (I).

The compounds of formula (I), wherein R¹, R², R³, R⁴, R⁵, X and n are asdefined for formula (I), can be obtained by transformation of a compoundof formula (II), wherein R³, R⁴, R⁵, X and n are as defined for formula(I), by several known methods among which the most widely uses are thefollowing:

-   -   a) Treatment with a compound of formula (III-a), wherein R¹ and        R² are as defined for formula (I) and R⁶ is C₁-C₄alkyl, in an        organic solvent such as toluene or methanol at temperatures        between 0° C. and 100° C.    -   b) Treatment with an orthoester of formula (III-b), wherein R⁶        is C₁-C₄alkyl, followed by treatment with an amine of formula        (III-c), wherein R¹ and R² are as defined for formula (I), in an        organic solvent such as methanol at temperatures between 20° C.        and 100° C.    -   c) Treatment with a formamide of formula (III-d), wherein R¹ and        R² are as defined for formula (I), and an activating agent such        as POCl₃ in an inert solvent such as dichloromethane at        temperatures between −20° C. and 40° C.        This is shown in Scheme 1 below.

Compounds of formula (II), wherein R³, X and n are as defined forformula (I) and R⁴ and R⁵ are hydrogen, can be obtained bytransformation of a compound of formula (IV), wherein R³, X and n are asdefined for formula (I), under reductive conditions, e.g. by catalytichydrogenation. This is shown in Scheme 2 below.

Compounds of formula (IV), wherein R³, X and n are as defined forformula (I), can be obtained by transformation of a compound of formula(V), wherein R³, X and n are as defined for formula (I), with atransition metal catalyst system under the conditions of the olefinmetathesis. This is shown in Scheme 3 below.

Compounds of formula (V), wherein R³ and X are as defined for formula(I) and n is 1, can be obtained by transformation of a compound offormula (VI), wherein R³ and X are as defined for formula (I), with acompound of formula (VII), wherein R⁷ is halogen, preferably chloro orbromo and with a base. This is shown in Scheme 4 below.

Alternatively, the compounds of formula (I), wherein R¹, R², R³, X and nare as defined for formula (I) and R⁴ and R⁵ are hydrogen, can beobtained by transformation of a compound of formula (VIII), wherein R¹,R², R³, X and n are as defined for formula (I), under reductiveconditions, e.g. by catalytic hydrogenation. This is shown in Scheme 5below.

The compounds of formula (VIII), wherein R¹, R², R³, X and n are asdefined for formula (I) can be obtained by transformation of a compoundof formula (IX), wherein R¹, R², R³, X and n are as defined for formula(I), with a transition metal catalyst system under the conditions of theolefin metathesis. This is shown in Scheme 6 below.

Compounds of formula (IX), wherein R¹, R², R³ and X are as defined forformula (I) and n is 1, can be obtained by transformation of a compoundof formula (X), wherein R¹, R², R³ and X are as defined for formula (I),with a compound of formula (VII), wherein R⁷ is halogen, preferablychloro or bromo and with a base. This is shown in Scheme 7 below.

Compounds of formula (X), wherein R¹, R², R³ and X are as defined forformula (I), can be obtained by transformation of a compound of formula(XI), wherein R¹, R², R³ and X are as defined for formula (I), with acompound of formula (XII), wherein R⁸ is MgBr or Li. This is shown inScheme 8 below.

Compounds of formula (XI), wherein R¹, R² and R³are as defined forformula (I) and X is O, can be obtained by transformation of a compoundof formula (XIII), wherein R¹, R² and R³ are as defined for formula (I)and R⁷ is halogen, preferably bromo or iodo, with a compound of formula(XIV) and with a strong base, such as butyl lithium. This is shown inScheme 9 below.

The compounds of formula (XIII), wherein R¹, R² and R³are as defined forformula (I) and R⁷ is halogen, preferably bromo or iodo, can be obtainedby transformation of a compound of formula (XV), wherein R³ is asdefined for formula (I) and R⁷ is halogen, preferably bromo or iodo, byseveral known methods among which the most widely uses are thefollowing:

-   -   a) Treatment with a compound of formula (III-a), wherein R¹ and        R² are as defined for formula (I) and R⁶ is C₁-C₄alkyl, in an        organic solvent such as toluene or methanol at temperatures        between 0° C. and 100° C.    -   b) Treatment with an orthoester of formula (III-b), wherein R⁶        is C₁-C₄alkyl, followed by treatment with an amine of formula        (III-c), wherein R¹ and R² are as defined for formula (I), in an        organic solvent such as methanol at temperatures between 20° C.        and 100° C.    -   c) Treatment with a formamide of formula (III-d), wherein R¹ and        R² are as defined for formula (I), and an activating agent such        as POCl₃in an inert solvent such as dichloromethane at        temperatures between −20° C. and 40° C.        This is shown in Scheme 10 below.

The compounds of formula (XV), wherein R³ is as defined for formula (I)and R⁷ is halogen, preferably bromo or iodo, can be obtained bytransformation of a compound of formula (XVI), wherein R³ is as definedfor formula (I) with a halogenation agent, such as bromine,N-bromosuccinimide or N-iodosuccinimide. This is shown in Scheme 11below.

The compounds of formula (XVI), wherein R³ is as defined for formula(I), can be obtained by transformation of a compound of formula (XVII),wherein R³ is as defined for formula (I), under reductive conditions,e.g. by catalytic hydrogenation or under conditions of the Bechampreaction. This is shown in Scheme 12 below.

The compounds of formula (XVII), wherein R³ is as defined for formula(I), can be obtained by transformation of a compound of formula (XVIII),wherein R³ is as defined for formula (I), with methyl bromide or methyliodide and with a base such as sodium hydride or potassium carbonate.This is shown in Scheme 13 below.

Certain intermediates described in the above schemes are novel and assuch form a further aspect of the invention.

The compounds of formula (I) can be used in the agricultural sector andrelated fields of use e.g. as active ingredients for controlling plantpests or on non-living materials for control of spoilage microorganismsor organisms potentially harmful to man. The novel compounds aredistinguished by excellent activity at low rates of application, bybeing well tolerated by plants and by being environmentally safe. Theyhave very useful curative, preventive and systemic properties and may beused for protecting numerous cultivated plants. The compounds of formula(I) can be used to inhibit or destroy the pests that occur on plants orparts of plants (fruit, blossoms, leaves, stems, tubers, roots) ofdifferent crops of useful plants, while at the same time protecting alsothose parts of the plants that grow later e.g. from phytopathogenicmicroorganisms.

It is also possible to use compounds of formula (I) as fungicide. Theterm “fungicide” as used herein means a compound that controls,modifies, or prevents the growth of fungi. The term “fungicidallyeffective amount” means the quantity of such a compound or combinationof such compounds that is capable of producing an effect on the growthof fungi. Controlling or modifying effects include all deviation fromnatural development, such as killing, retardation and the like, andprevention includes barrier or other defensive formation in or on aplant to prevent fungal infection.

It is also possible to use compounds of formula (I) as dressing agentsfor the treatment of plant propagation material, e.g., seed, such asfruits, tubers or grains, or plant cuttings (for example rice), for theprotection against fungal infections as well as against phytopathogenicfungi occurring in the soil. The propagation material can be treatedwith a composition comprising a compound of formula (I) before planting:seed, for example, can be dressed before being sown. The compounds offormula (I) can also be applied to grains (coating), either byimpregnating the seeds in a liquid formulation or by coating them with asolid formulation. The composition can also be applied to the plantingsite when the propagation material is being planted, for example, to theseed furrow during sowing. The invention relates also to such methods oftreating plant propagation material and to the plant propagationmaterial so treated.

Furthermore the compounds according to present invention can be used forcontrolling fungi in related areas, for example in the protection oftechnical materials, including wood and wood related technical products,in food storage, in hygiene management.

In addition, the invention could be used to protect non-living materialsfrom fungal attack, e.g. lumber, wall boards and paint.

Compounds of formula (I) and fungicidal compositions containing them maybe used to control plant diseases caused by a broad spectrum of fungalplant pathogens. They are effective in controlling a broad spectrum ofplant diseases, such as foliar pathogens of ornamental, turf, vegetable,field, cereal, and fruit crops.

These fungi and fungal vectors of disease, as well as phytopathogenicbacteria and viruses, which may be controlled are for example:

Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp,Aspergillus spp. including A. flavus, A. fumigatus, A. nidulans, A.niger, A. terrus, Aureobasidium spp. including A. pullulans, Blastomycesdermatitidis, Blumeria graminis, Bremia lactucae, Botryosphaeria spp.including B. dothidea, B. obtusa, Botrytis spp. including B. cinerea,Candida spp. including C. albicans, C. glabrata, C. krusei, C.lusitaniae, C. parapsilosis, C. tropicalis, Cephaloascus fragrans,Ceratocystis spp, Cercospora spp. including C. arachidicola,Cercosporidium personatum, Cladosporium spp, Claviceps purpurea,Coccidioides immitis, Cochliobolus spp, Colletotrichum spp. including C.musae, Cryptococcus neoformans, Diaporthe spp, Didymella spp, Drechsleraspp, Elsinoe spp, Epidermophyton spp, Erwinia amylovora, Erysiphe spp.including E. cichoracearum, Eutypa lata, Fusarium spp. including F.culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum,F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis,Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum,Glomerella cingulate, Guignardia bidwellii, Gymnosporangiumjuniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasmaspp. including H. capsulatum, Laetisaria fuciformis, Leptographiumlindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochiumnivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp.including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostomapiceae, Paracoccidioides spp, Penicillium spp. including P. digitatum,P. italicum, Petriellidium spp, Peronosclerospora spp. Including P.maydis, P. philippinensis and P. sorghi, Peronospora spp, Phaeosphaerianodorum, Phakopsora pachyrhizi, Phellinus igniarus, Phialophora spp,Phoma spp, Phomopsis viticola, Phytophthora spp. including P. infestans,Plasmopara spp. including P. halstedii, P. viticola, Pleospora spp.,Podosphaera spp. including P. leucotricha, Polymyxa graminis, Polymyxabetae, Pseudocercosporella herpotrichoides, Pseudomonas spp,Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopezizatracheiphila, Puccinia Spp. including P. hordei, P. recondita, P.striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp,Pyricularia spp. including P. oryzae, Pythium spp. including P. ultimum,Ramularia spp, Rhizoctonia spp, Rhizomucor pusillus, Rhizopus arrhizus,Rhynchosporium spp, Scedosporium spp. including S. apiospermum and S.prolificans, Schizothyrium pomi, Sclerotinia spp, Sclerotium spp,Septoria spp, including S. nodorum, S. tritici, Sphaerotheca macularis,Sphaerotheca fusca (Sphaerotheca fuliginea), Sporothorix spp,Stagonospora nodorum, Stemphylium spp,. Stereum hirsutum, Thanatephoruscucumeris, Thielaviopsis basicola, Tilletia spp, Trichoderma spp.including T. harzianum, T. pseudokoningii, T. viride, Trichophyton spp,Typhula spp, Uncinula necator, Urocystis spp, Ustilago spp, Venturiaspp. including V. inaequalis, Verticillium spp, and Xanthomonas spp.

In particular, compounds of formula (I) and fungicidal compositionscontaining them may be used to control plant diseases caused by a broadspectrum of fungal plant pathogens in the Basidiomycete, Ascomycete,Oomycete and/or Deuteromycete, Blasocladiomycete, Chrytidiomycete,Glomeromycete and/or Mucoromycete classes.

These pathogens may include:

Oomycetes, including Phytophthora diseases such as those caused byPhytophthora capsici, Phytophthora infestans, Phytophthora sojae,Phytophthora fragariae, Phytophthora nicotianae, Phytophthora cinnamomi,Phytophthora citricola, Phytophthora citrophthora and Phytophthoraerythroseptica; Pythium diseases such as those caused by Pythiumaphanidermatum, Pythium arrhenomanes, Pythium graminicola, Pythiumirregulare and Pythium ultimum; diseases caused by Peronosporales suchas Peronospora destructor, Peronospora parasitica, Plasmopara viticola,Plasmopara halstedii, Pseudoperonospora cubensis, Albugo candida,Sclerophthora macrospora and Bremia lactucae; and others such asAphanomyces cochlioides, Labyrinthula zosterae, Peronosclerospora sorghiand Sclerospora graminicola. Ascomycetes, including blotch, spot, blastor blight diseases and/or rots for example those caused by Pleosporalessuch as Stemphylium solani, Stagonospora tainanensis, Spilocaeaoleaginea, Setosphaeria turcica, Pyrenochaeta lycoperisici, Pleosporaherbarum, Phoma destructiva, Phaeosphaeria herpotrichoides,Phaeocryptocus gaeumannii, Ophiosphaerella graminicola, Ophiobolusgraminis, Leptosphaeria maculans, Hendersonia creberrima,Helminthosporium triticirepentis, Setosphaeria turcica, Drechsleraglycines, Didymella bryoniae, Cycloconium oleagineum, Corynesporacassiicola, Cochliobolus sativus, Bipolaris cactivora, Venturiainaequalis, Pyrenophora teres, Pyrenophora tritici-repentis, Alternariaalternata, Alternaria brassicicola, Alternaria solani and Alternariatomatophila, Capnodiales such as Septoria tritici, Septoria nodorum,Septoria glycines, Cercospora arachidicola, Cercospora sojina,Cercospora zeae-maydis, Cercosporella capsellae and Cercosporellaherpotrichoides, Cladosporium carpophilum, Cladosporium effusum,Passalora fulva, Cladosporium oxysporum, Dothistroma septosporum,Isariopsis clavispora, Mycosphaerella fijiensis, Mycosphaerellagraminicola, Mycovellosiella koepkeii, Phaeoisariopsis bataticola,Pseudocercospora vitis, Pseudocercosporella herpotrichoides, Ramulariabeticola, Ramularia collo-cygni, Magnaporthales such as Gaeumannomycesgraminis, Magnaporthe grisea, Pyricularia oryzae, Diaporthales such asAnisogramma anomala, Apiognomonia errabunda, Cytospora platani,Diaporthe phaseolorum, Discula destructiva, Gnomonia fructicola,Greeneria uvicola, Melanconium juglandinum, Phomopsis viticola,Sirococcus clavigignenti-juglandacearum, Tubakia dryina, Dicarpellaspp., Valsa ceratosperma, and others such as Actinothyrium graminis,Ascochyta pisi, Aspergillus flavus, Aspergillus fumigatus, Aspergillusnidulans, Asperisporium caricae, Blumeriella jaapii, Candida spp.,Capnodium ramosum, Cephaloascus spp., Cephalosporium gramineum,Ceratocystis paradoxa, Chaetomium spp., Hymenoscyphus pseudoalbidus,Coccidioides spp., Cylindrosporium padi, Diplocarpon malae,Drepanopeziza campestris, Elsinoe ampelina, Epicoccum nigrum,Epidermophyton spp., Eutypa lata, Geotrichum candidum, Gibellinacerealis, Gloeocercospora sorghi, Gloeodes pomigena, Gloeosporiumperennans; Gloeotinia temulenta, Griphospaeria corticola, Kabatiellalini, Leptographium microsporum, Leptosphaerulinia crassiasca,Lophodermium seditiosum, Marssonina graminicola, Microdochium nivale,Monilinia fructicola, Monographella albescens, Monosporascuscannonballus, Naemacyclus spp., Ophiostoma novo-ulmi, Paracoccidioidesbrasiliensis, Penicillium expansum, Pestalotia rhododendri,Petriellidium spp., Pezicula spp., Phialophora gregata, Phyllachorapomigena, Phymatotrichum omnivora, Physalospora abdita, Plectosporiumtabacinum, Polyscytalum pustulans, Pseudopeziza medicaginis,Pyrenopeziza brassicae, Ramulispora sorghi, Rhabdocline pseudotsugae,Rhynchosporium secalis, Sacrocladium oryzae, Scedosporium spp.,Schizothyrium pomi, Sclerotinia sclerotiorum, Sclerotinia minor,Sclerotium spp., Typhula ishikariensis, Seimatosporium mariae,Lepteutypa cupressi, Septocyta ruborum, Sphaceloma perseae, Sporonemaphacidioides, Stigmina palmivora, Tapesia yallundae, Taphrina bullata,Thielviopsis basicola, Trichoseptoria fructigena, Zygophialajamaicensis; powdery mildew diseases for example those caused byErysiphales such as Blumeria graminis, Erysiphe polygoni, Uncinulanecator, Sphaerotheca fuligena, Podosphaera leucotricha, Podospaeramacularis Golovinomyces cichoracearum, Leveillula taurica, Microsphaeradiffusa, Oidiopsis gossypii, Phyllactinia guttata and Oidium arachidis;molds for example those caused by Botryosphaeriales such as Dothiorellaaromatica, Diplodia seriata, Guignardia bidwellii, Botrytis cinerea,Botryotinia allii, Botryotinia fabae, Fusicoccum amygdali, Lasiodiplodiatheobromae, Macrophoma theicola, Macrophomina phaseolina, Phyllostictacucurbitacearum; anthracnoses for example those caused by Glommerelalessuch as Colletotrichum gloeosporioides, Colletotrichum lagenarium,Colletotrichum gossypii, Glomerella cingulata, and Colletotrichumgraminicola; and wilts or blights for example those caused byHypocreales such as Acremonium strictum, Claviceps purpurea, Fusariumculmorum, Fusarium graminearum, Fusarium virguliforme, Fusariumoxysporum, Fusarium subglutinans, Fusarium oxysporum f.sp. cubense,Gerlachia nivale, Gibberella fujikuroi, Gibberella zeae, Gliocladiumspp., Myrothecium verrucaria, Nectria ramulariae, Trichoderma viride,Trichothecium roseum, and Verticillium theobromae.

Basidiomycetes, including smuts for example those caused byUstilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilagotritici, Ustilago zeae, rusts for example those caused by Puccinialessuch as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporiumipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata,Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei,Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp. Secalis,Pucciniastrum coryli, or Uredinales such as Cronartium ribicola,Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsorapachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzscheliadiscolor and Uromyces viciae-fabae; and other rots and diseases such asthose caused by Cryptococcus spp., Exobasidium vexans, Marasmiellusinoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis,Urocystis agropyri, Itersonilia perplexans, Corticium invisum,Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani,Thanetephorus cucurmeris, Entyloma dahliae, Entylomella microspora,Neovossia moliniae and Tilletia caries.

Blastocladiomycetes, such as Physoderma maydis.

Mucoromycetes, such as Choanephora cucurbitarum.; Mucor spp.; Rhizopusarrhizus,

As well as diseases caused by other species and genera closely relatedto those listed above.

In addition to their fungicidal activity, the compounds and compositionscomprising them may also have activity against bacteria such as Erwiniaamylovora, Erwinia caratovora, Xanthomonas campestris, Pseudomonassyringae, Strptomyces scabies and other related species as well ascertain protozoa.

Within the scope of present invention, target crops and/or useful plantsto be protected typically comprise perennial and annual crops, such asberry plants for example blackberries, blueberries, cranberries,raspberries and strawberries; cereals for example barley, maize (corn),millet, oats, rice, rye, sorghum triticale and wheat; fibre plants forexample cotton, flax, hemp, jute and sisal; field crops for examplesugar and fodder beet, coffee, hops, mustard, oilseed rape (canola),poppy, sugar cane, sunflower, tea and tobacco; fruit trees for exampleapple, apricot, avocado, banana, cherry, citrus, nectarine, peach, pearand plum; grasses for example Bermuda grass, bluegrass, bentgrass,centipede grass, fescue, ryegrass, St. Augustine grass and Zoysia grass;herbs such as basil, borage, chives, coriander, lavender, lovage, mint,oregano, parsley, rosemary, sage and thyme; legumes for example beans,lentils, peas and soya beans; nuts for example almond, cashew, groundnut, hazelnut, peanut, pecan, pistachio and walnut; palms for exampleoil palm; ornamentals for example flowers, shrubs and trees; othertrees, for example cacao, coconut, olive and rubber; vegetables forexample asparagus, aubergine, broccoli, cabbage, carrot, cucumber,garlic, lettuce, marrow, melon, okra, onion, pepper, potato, pumpkin,rhubarb, spinach and tomato; and vines for example grapes.

The useful plants and/or target crops in accordance with the inventioninclude conventional as well as genetically enhanced or engineeredvarieties such as, for example, insect resistant (e.g. Bt. and VIPvarieties) as well as disease resistant, herbicide tolerant (e.g.glyphosate- and glufosinate-resistant maize varieties commerciallyavailable under the trade names RoundupReady® and LibertyLink®) andnematode tolerant varieties. By way of example, suitable geneticallyenhanced or engineered crop varieties include the Stoneville 5599BRcotton and Stoneville 4892BR cotton varieties.

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants that have been rendered tolerant toherbicides like bromoxynil or classes of herbicides (such as, forexample, HPPD inhibitors, ALS inhibitors, for example primisulfuron,prosulfuron and trifloxysulfuron, EPSPS(5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS(glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase)inhibitors) as a result of conventional methods of breeding or geneticengineering. An example of a crop that has been rendered tolerant toimidazolinones, e.g. imazamox, by conventional methods of breeding(mutagenesis) is Clearfield® summer rape (Canola). Examples of cropsthat have been rendered tolerant to herbicides or classes of herbicidesby genetic engineering methods include glyphosate- andglufosinate-resistant maize varieties commercially available under thetrade names RoundupReady®, Herculex I® and LibertyLink®.

The term “useful plants” and/or “target crops” is to be understood asincluding those which naturally are or have been rendered resistant toharmful insects. This includes plants transformed by the use ofrecombinant DNA techniques, for example, to be capable of synthesisingone or more selectively acting toxins, such as are known, for example,from toxin-producing bacteria. Examples of toxins which can be expressedinclude δ-endotoxins, vegetative insecticidal proteins (Vip),insecticidal proteins of bacteria colonising nematodes, and toxinsproduced by scorpions, arachnids, wasps and fungi. An example of a cropthat has been modified to express the Bacillus thuringiensis toxin isthe Bt maize KnockOut® (Syngenta Seeds). An example of a crop comprisingmore than one gene that codes for insecticidal resistance and thusexpresses more than one toxin is VipCot® (Syngenta Seeds). Crops or seedmaterial thereof can also be resistant to multiple types of pests(so-called stacked transgenic events when created by geneticmodification). For example, a plant can have the ability to express aninsecticidal protein while at the same time being herbicide tolerant,for example Herculex I® (Dow AgroSciences, Pioneer Hi-BredInternational).

The term “useful plants” and/or “target crops” is to be understood asincluding also useful plants which have been so transformed by the useof recombinant DNA techniques that they are capable of synthesisingantipathogenic substances having a selective action, such as, forexample, the so-called “pathogenesis-related proteins” (PRPs, see e.g.EP-A-0 392 225). Examples of such antipathogenic substances andtransgenic plants capable of synthesising such antipathogenic substancesare known, for example, from EP-A-0 392 225, WO 95/33818, and EP-A-0 353191. The methods of producing such transgenic plants are generally knownto the person skilled in the art and are described, for example, in thepublications mentioned above.

Toxins that can be expressed by transgenic plants include, for example,insecticidal proteins from Bacillus cereus or Bacillus popilliae; orinsecticidal proteins from Bacillus thuringiensis, such as δ-endotoxins,e.g. Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2, Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, orvegetative insecticidal proteins (Vip), e.g. Vip1, Vip2, Vip3 or Vip3A;or insecticidal proteins of bacteria colonising nematodes, for examplePhotorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens,Xenorhabdus nematophilus; toxins produced by animals, such as scorpiontoxins, arachnid toxins, wasp toxins and other insect-specificneurotoxins; toxins produced by fungi, such as Streptomycetes toxins,plant lectins, such as pea lectins, barley lectins or snowdrop lectins;agglutinins; proteinase inhibitors, such as trypsin inhibitors, serineprotease inhibitors, patatin, cystatin, papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ionchannel blockers, such as blockers of sodium or calcium channels,juvenile hormone esterase, diuretic hormone receptors, stilbenesynthase, bibenzyl synthase, chitinases and glucanases.

Further, in the context of the present invention there are to beunderstood by δ-endotoxins, for example Cry1Ab, Cry1Ac, Cry1F, Cry1Fa2,Cry2Ab, Cry3A, Cry3Bb1 or Cry9C, or vegetative insecticidal proteins(Vip), for example Vip1, Vip2, Vip3 or Vip3A, expressly also hybridtoxins, truncated toxins and modified toxins. Hybrid toxins are producedrecombinantly by a new combination of different domains of thoseproteins (see, for example, WO 02/15701). Truncated toxins, for examplea truncated Cry1Ab, are known. In the case of modified toxins, one ormore amino acids of the naturally occurring toxin are replaced. In suchamino acid replacements, preferably non-naturally present proteaserecognition sequences are inserted into the toxin, such as, for example,in the case of Cry3A055, a cathepsin-G-recognition sequence is insertedinto a Cry3A toxin (see WO03/018810).

More examples of such toxins or transgenic plants capable ofsynthesising such toxins are disclosed, for example, in EP-A-0 374 753,WO93/07278, WO95/34656, EP-A-0 427 529, EP-A-451 878 and WO03/052073.

The processes for the preparation of such transgenic plants aregenerally known to the person skilled in the art and are described, forexample, in the publications mentioned above. Cryl-type deoxyribonucleicacids and their preparation are known, for example, from WO 95/34656,EP-A-0 367 474, EP-A-0 401 979 and WO 90/13651.

The toxin contained in the transgenic plants imparts to the plantstolerance to harmful insects. Such insects can occur in any taxonomicgroup of insects, but are especially commonly found in the beetles(Coleoptera), two-winged insects (Diptera) and butterflies(Lepidoptera).

Transgenic plants containing one or more genes that code for aninsecticidal resistance and express one or more toxins are known andsome of them are commercially available. Examples of such plants are:YieldGard® (maize variety that expresses a Cry1Ab toxin); YieldGardRootworm® (maize variety that expresses a Cry3Bb1 toxin); YieldGardPlus® (maize variety that expresses a Cry1Ab and a Cry3Bb1 toxin);Starlink® (maize variety that expresses a Cry9C toxin); Herculex I®(maize variety that expresses a Cry1Fa2 toxin and the enzymephosphinothricine N-acetyltransferase (PAT) to achieve tolerance to theherbicide glufosinate ammonium); NuCOTN 33B® (cotton variety thatexpresses a Cry1Ac toxin); Bollgard I® (cotton variety that expresses aCry1Ac toxin); Bollgard II® (cotton variety that expresses a Cry1Ac anda Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and aCry1Ab toxin); NewLeaf® (potato variety that expresses a Cry3A toxin);NatureGard®, Agrisure® GT Advantage (GA21 glyphosate-tolerant trait),Agrisure® CB Advantage (Bt11 corn borer (CB) trait) and Protecta®.

Further examples of such transgenic crops are:

1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a truncated Cry1Ab toxin. Bt11 maize alsotransgenically expresses the enzyme PAT to achieve tolerance to theherbicide glufosinate ammonium.

2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Geneticallymodified Zea mays which has been rendered resistant to attack by theEuropean corn borer (Ostrinia nubilalis and Sesamia nonagrioides) bytransgenic expression of a Cry1Ab toxin. Bt176 maize also transgenicallyexpresses the enzyme PAT to achieve tolerance to the herbicideglufosinate ammonium.

3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790St. Sauveur, France, registration number C/FR/96/05/10. Maize which hasbeen rendered insect-resistant by transgenic expression of a modifiedCry3A toxin. This toxin is Cry3A055 modified by insertion of acathepsin-G-protease recognition sequence. The preparation of suchtransgenic maize plants is described in WO 03/018810.

4. MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863expresses a Cry3Bb1 toxin and has resistance to certain Coleopterainsects.

5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren,B-1150 Brussels, Belgium, registration number C/ES/96/02.

6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7B-1160 Brussels, Belgium, registration number C/NL/00/10. Geneticallymodified maize for the expression of the protein Cry1F for achievingresistance to certain Lepidoptera insects and of the PAT protein forachieving tolerance to the herbicide glufosinate ammonium.

7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de 20Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03.Consists of conventionally bred hybrid maize varieties by crossing thegenetically modified varieties NK603 and MON 810. NK603 x MON 810 Maizetransgenically expresses the protein CP4 EPSPS, obtained fromAgrobacterium sp. strain CP4, which imparts tolerance to the herbicideRoundup® (contains glyphosate), and also a Cry1Ab toxin obtained fromBacillus thuringiensis subsp. kurstaki which brings about tolerance tocertain Lepidoptera, include the European corn borer.

The term “locus” as used herein means fields in or on which plants aregrowing, or where seeds of cultivated plants are sown, or where seedwill be placed into the soil. It includes soil, seeds, and seedlings, aswell as established vegetation.

The term “plants” refers to all physical parts of a plant, includingseeds, seedlings, saplings, roots, tubers, stems, stalks, foliage, andfruits.

The term “plant propagation material” is understood to denote generativeparts of the plant, such as seeds, which can be used for themultiplication of the latter, and vegetative material, such as cuttingsor tubers, for example potatoes. There may be mentioned for exampleseeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes andparts of plants. Germinated plants and young plants which are to betransplanted after germination or after emergence from the soil, mayalso be mentioned. These young plants may be protected beforetransplantation by a total or partial treatment by immersion. Preferably“plant propagation material” is understood to denote seeds.

Pesticidal agents referred to herein using their common name are known,for example, from “The Pesticide Manual”, 15th Ed., British CropProtection Council 2009.

The compounds of formula (I) may be used in unmodified form or,preferably, together with the adjuvants conventionally employed in theart of formulation. To this end they may be conveniently formulated inknown manner to emulsifiable concentrates, coatable pastes, directlysprayable or dilutable solutions or suspensions, dilute emulsions,wettable powders, soluble powders, dusts, granulates, and alsoencapsulations e.g. in polymeric substances. As with the type of thecompositions, the methods of application, such as spraying, atomising,dusting, scattering, coating or pouring, are chosen in accordance withthe intended objectives and the prevailing circumstances. Thecompositions may also contain further adjuvants such as stabilizers,antifoams, viscosity regulators, binders or tackifiers as well asfertilizers, micronutrient donors or other formulations for obtainingspecial effects.

Suitable carriers and adjuvants, e.g. for agricultural use, can be solidor liquid and are substances useful in formulation technology, e.g.natural or regenerated mineral substances, solvents, dispersants,wetting agents, tackifiers, thickeners, binders or fertilizers. Suchcarriers are for example described in WO 97/33890.

Suspension concentrates are aqueous formulations in which finely dividedsolid particles of the active compound are suspended. Such formulationsinclude anti-settling agents and dispersing agents and may furtherinclude a wetting agent to enhance activity as well an anti-foam and acrystal growth inhibitor. In use, these concentrates are diluted inwater and normally applied as a spray to the area to be treated. Theamount of active ingredient may range from 0.5% to 95% of theconcentrate.

Wettable powders are in the form of finely divided particles whichdisperse readily in water or other liquid carriers. The particlescontain the active ingredient retained in a solid matrix. Typical solidmatrices include fuller's earth, kaolin clays, silicas and other readilywet organic or inorganic solids. Wettable powders normally contain from5% to 95% of the active ingredient plus a small amount of wetting,dispersing or emulsifying agent.

Emulsifiable concentrates are homogeneous liquid compositionsdispersible in water or other liquid and may consist entirely of theactive compound with a liquid or solid emulsifying agent, or may alsocontain a liquid carrier, such as xylene, heavy aromatic naphthas,isophorone and other non-volatile organic solvents. In use, theseconcentrates are dispersed in water or other liquid and normally appliedas a spray to the area to be treated. The amount of active ingredientmay range from 0.5% to 95% of the concentrate.

Granular formulations include both extrudates and relatively coarseparticles and are usually applied without dilution to the area in whichtreatment is required. Typical carriers for granular formulationsinclude sand, fuller's earth, attapulgite clay, bentonite clays,montmorillonite clay, vermiculite, perlite, calcium carbonate, brick,pumice, pyrophyllite, kaolin, dolomite, plaster, wood flour, ground corncobs, ground peanut hulls, sugars, sodium chloride, sodium sulphate,sodium silicate, sodium borate, magnesia, mica, iron oxide, zinc oxide,titanium oxide, antimony oxide, cryolite, gypsum, diatomaceous earth,calcium sulphate and other organic or inorganic materials which absorbor which can be coated with the active compound. Granular formulationsnormally contain 5% to 25% of active ingredients which may includesurface-active agents such as heavy aromatic naphthas, kerosene andother petroleum fractions, or vegetable oils; and/or stickers such asdextrins, glue or synthetic resins.

Dusts are free-flowing admixtures of the active ingredient with finelydivided solids such as talc, clays, flours and other organic andinorganic solids which act as dispersants and carriers.

Microcapsules are typically droplets or granules of the activeingredient enclosed in an inert porous shell which allows escape of theenclosed material to the surroundings at controlled rates. Encapsulateddroplets are typically 1 to 50 microns in diameter. The enclosed liquidtypically constitutes 50 to 95% of the weight of the capsule and mayinclude solvent in addition to the active compound. Encapsulatedgranules are generally porous granules with porous membranes sealing thegranule pore openings, retaining the active species in liquid forminside the granule pores. Granules typically range from 1 millimetre to1 centimetre and preferably 1 to 2 millimetres in diameter. Granules areformed by extrusion, agglomeration or prilling, or are naturallyoccurring. Examples of such materials are vermiculite, sintered clay,kaolin, attapulgite clay, sawdust and granular carbon. Shell or membranematerials include natural and synthetic rubbers, cellulosic materials,styrene-butadiene copolymers, polyacrylonitriles, polyacrylates,polyesters, polyamides, polyureas, polyurethanes and starch xanthates.

Other useful formulations for agrochemical applications include simplesolutions of the active ingredient in a solvent in which it iscompletely soluble at the desired concentration, such as acetone,alkylated naphthalenes, xylene and other organic solvents. Pressurisedsprayers, wherein the active ingredient is dispersed in finely-dividedform as a result of vaporisation of a low boiling dispersant solventcarrier, may also be used.

Suitable agricultural adjuvants and carriers that are useful informulating the compositions of the invention in the formulation typesdescribed above are well known to those skilled in the art.

Liquid carriers that can be employed include, for example, water,toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethylketone, cyclohexanone, acetic anhydride, acetonitrile, acetophenone,amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol,alkyl acetates, diacetonalcohol, 1,2-dichloropropane, diethanolamine,p-diethylbenzene, diethylene glycol, diethylene glycol abietate,diethylene glycol butyl ether, diethylene glycol ethyl ether, diethyleneglycol methyl ether, N,N-dimethyl formamide, dimethyl sulfoxide,1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether,dipropylene glycol dibenzoate, diproxitol, alkyl pyrrolidinone, ethylacetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane,2-heptanone, alpha pinene, d-limonene, ethylene glycol, ethylene glycolbutyl ether, ethylene glycol methyl ether, gamma-butyrolactone,glycerol, glycerol diacetate, glycerol monoacetate, glycerol triacetate,hexadecane, hexylene glycol, isoamyl acetate, isobornyl acetate,isooctane, isophorone, isopropyl benzene, isopropyl myristate, lacticacid, laurylamine, mesityl oxide, methoxy-propanol, methyl isoamylketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, methyloleate, methylene chloride, m-xylene, n-hexane, n-octylamine,octadecanoic acid, octyl amine acetate, oleic acid, oleylamine,o-xylene, phenol, polyethylene glycol (PEG400), propionic acid,propylene glycol, propylene glycol monomethyl ether, p-xylene, toluene,triethyl phosphate, triethylene glycol, xylene sulfonic acid, paraffin,mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amylacetate, butyl acetate, methanol, ethanol, isopropanol, and highermolecular weight alcohols such as amyl alcohol, tetrahydrofurfurylalcohol, hexanol, octanol, etc., ethylene glycol, propylene glycol,glycerine and N-methyl-2-pyrrolidinone. Water is generally the carrierof choice for the dilution of concentrates.

Suitable solid carriers include, for example, talc, titanium dioxide,pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk,diatomaxeous earth, lime, calcium carbonate, bentonite clay, fuller'searth, cotton seed hulls, wheat flour, soybean flour, pumice, woodflour, walnut shell flour and lignin.

A broad range of surface-active agents are advantageously employed inboth said liquid and solid compositions, especially those designed to bediluted with carrier before application. These agents, when used,normally comprise from 0.1% to 15% by weight of the formulation. Theycan be anionic, cationic, non-ionic or polymeric in character and can beemployed as emulsifying agents, wetting agents, suspending agents or forother purposes. Typical surface active agents include salts of alkylsulfates, such as diethanolammonium lauryl sulphate; alkylarylsulfonatesalts, such as calcium dodecylbenzenesulfonate; alkylphenol-alkyleneoxide addition products, such as nonylphenol-C.sub. 18 ethoxylate;alcohol-alkylene oxide addition products, such as tridecylalcohol-C.sub. 16 ethoxylate; soaps, such as sodium stearate;alkylnaphthalenesulfonate salts, such as sodiumdibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts,such as sodium di(2-ethylhexyl) sulfosuccinate; sorbitol esters, such assorbitol oleate; quaternary amines, such as lauryl trimethylammoniumchloride; polyethylene glycol esters of fatty acids, such aspolyethylene glycol stearate; block copolymers of ethylene oxide andpropylene oxide; and salts of mono and dialkyl phosphate esters.

Other adjuvants commonly utilized in agricultural compositions includecrystallisation inhibitors, viscosity modifiers, suspending agents,spray droplet modifiers, pigments, antioxidants, foaming agents,anti-foaming agents, light-blocking agents, compatibilizing agents,antifoam agents, sequestering agents, neutralising agents and buffers,corrosion inhibitors, dyes, odorants, spreading agents, penetrationaids, micronutrients, emollients, lubricants and sticking agents.

In addition, further, other biocidally active ingredients orcompositions may be combined with the compositions of the invention andused in the methods of the invention and applied simultaneously orsequentially with the compositions of the invention. When appliedsimultaneously, these further active ingredients may be formulatedtogether with the compositions of the invention or mixed in, forexample, the spray tank. These further biocidally active ingredients maybe fungicides, herbicides, insecticides, bactericides, acaricides,nematicides and/or plant growth regulators.

In addition, the compositions of the invention may also be applied withone or more systemically acquired resistance inducers (“SAR” inducer).SAR inducers are known and described in, for example, U.S. Pat. No.6,919,298 and include, for example, salicylates and the commercial SARinducer acibenzolar-S-methyl.

The compounds of formula (I) are normally used in the form ofcompositions and can be applied to the crop area or plant to be treated,simultaneously or in succession with further compounds. These furthercompounds can be e.g. fertilizers or micronutrient donors or otherpreparations, which influence the growth of plants. They can also beselective herbicides or non-selective herbicides as well asinsecticides, fungicides, bactericides, nematicides, molluscicides ormixtures of several of these preparations, if desired together withfurther carriers, surfactants or application promoting adjuvantscustomarily employed in the art of formulation.

The compounds of formula (I) may be used in the form of (fungicidal)compositions for controlling or protecting against phytopathogenicmicroorganisms, comprising as active ingredient at least one compound offormula (I) or of at least one preferred individual compound asabove-defined, in free form or in agrochemically usable salt form, andat least one of the above-mentioned adjuvants.

The invention therefore provides a composition, preferably a fungicidalcomposition, comprising at least one compound formula (I) anagriculturally acceptable carrier and optionally an adjuvant. Anagricultural acceptable carrier is for example a carrier that issuitable for agricultural use. Agricultural carriers are well known inthe art. Preferably said composition may comprise at least one or morepesticidally active compounds, for example an additional fungicidalactive ingredient in addition to the compound of formula (I).

The compound of formula (I) may be the sole active ingredient of acomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may, in some cases, result in unexpected synergisticactivities.

Examples of suitable additional active ingredients include thefollowing: 1,2,4-thiadiazoles, 2,6-dinitroanilines, acylalanines,aliphatic nitrogenous compounds, amidines, aminopyrimidinols, anilides,anilino-pyrimidines, anthraquinones, antibiotics, aryl-phenylketones,benzamides, benzene-sulfonamides, benzimidazoles, benzothiazoles,benzothiodiazoles, benzothiophenes, benzoylpyridines, benzthiadiazoles,benzylcarbamates, butylamines, carbamates, carboxamides, carpropamids,chloronitriles, cinnamic acid amides, copper containing compounds,cyanoacetamideoximes, cyanoacrylates, cyanoimidazoles,cyanomethylene-thiazolidines, dicarbonitriles, dicarboxamides,dicarboximides, dimethylsulphamates, dinitrophenol carbonates,dinitrophenysl, dinitrophenyl crotonates, diphenyl phosphates, dithiinocompounds, dithiocarbamates, dithioethers, dithiolanes,ethyl-amino-thiazole carboxamides, ethyl-phosphonates, furancarboxamides, glucopyranosyls, glucopyranoxyls, glutaronitriles,guanidines, herbicides/plant growth regulators, hexopyranosylantibiotics, hydroxy(2-amino)pyrimidines, hydroxyanilides,hydroxyisoxazoles, imidazoles, imidazolinones, insecticides/plant growthregulators, isobenzofuranones, isoxazolidinyl-pyridines, isoxazolines,maleimides, mandelic acid amides, mectin derivatives, morpholines,norpholines, n-phenyl carbamates, organotin compounds, oxathiincarboxamides, oxazoles, oxazolidine-diones, phenols, phenoxy quinolines,phenyl-acetamides, phenylamides, phenylbenzamides,phenyl-oxo-ethyl-thiophenes amides, phenylpyrroles, phenylureas,phosphorothiolates, phosphorus acids, phthalamic acids, phthalimides,picolinamides, piperazines, piperidines, plant extracts, polyoxins,propionamides, pthalimides, pyrazole-4-carboxamides, pyrazolinones,pyridazinones, pyridines, pyridine carboxamides, pyridinyl-ethylbenzamides, pyrimdinamines, pyrimidines, pyrimidine-amines,pyrimidione-hydrazone, pyrrolidines, pyrrolquinoliones, quinazolinones,quinolines, quinoline derivatives, quinoline-7-carboxylic acids,quinoxalines, spiroketalamines, strobilurins, sulfamoyl triazoles,sulphamides, tetrazolyloximes, thiadiazines, thiadiazole carboxamides,thiazole carboxanides, thiocyanates, thiophene carboxamides, toluamides,triazines, triazobenthiazoles, triazoles, triazole-thiones,triazolo-pyrimidylamine, valinamide carbamates, ammonium methylphosphonates, arsenic-containing compounds, benyimidazolylcarbamates,carbonitriles, carboxanilides, carboximidamides, carboxylicphenylamides, diphenyl pyridines, furanilides, hydrazine carboxamides,imidazoline acetates, isophthalates, isoxazolones, mercury salts,organomercury compounds, organophosphates, oxazolidinediones,pentylsulfonyl benzenes, phenyl benzamides, phosphonothionates,phosphorothioates, pyridyl carboxamides, pyridyl furfuryl ethers,pyridyl methyl ethers, SDHIs, thiadiazinanethiones, thiazolidines.

A further aspect of invention is related to a method of controlling orpreventing an infestation of plants, e.g. useful plants such as cropplants, propagation material thereof, e.g. seeds, harvested crops, e.g.harvested food crops, or of non-living materials by phytopathogenic orspoilage microorganisms or organisms potentially harmful to man,especially fungal organisms, which comprises the application of acompound of formula (I) or of a preferred individual compound asabove-defined as active ingredient to the plants, to parts of the plantsor to the locus thereof, to the propagation material thereof, or to anypart of the non-living materials.

Controlling or preventing means reducing infestation by insects or byphytopathogenic or spoilage microorganisms or organisms potentiallyharmful to man, especially fungal organisms, to such a level that animprovement is demonstrated.

A preferred method of controlling or preventing an infestation of cropplants by phytopathogenic microorganisms, especially fungal organisms,or insects which comprises the application of a compound of formula (I),or an agrochemical composition which contains at least one of saidcompounds, is foliar application. The frequency of application and therate of application will depend on the risk of infestation by thecorresponding pathogen or insect. However, the compounds of formula (I)can also penetrate the plant through the roots via the soil (systemicaction) by drenching the locus of the plant with a liquid formulation,or by applying the compounds in solid form to the soil, e.g. in granularform (soil application). In crops of water rice such granulates can beapplied to the flooded rice field. The compounds of formula (I) may alsobe applied to seeds (coating) by impregnating the seeds or tubers eitherwith a liquid formulation of the fungicide or coating them with a solidformulation.

A formulation, e.g. a composition containing the compound of formula(I), and, if desired, a solid or liquid adjuvant or monomers forencapsulating the compound of formula (I), may be prepared in a knownmanner, typically by intimately mixing and/or grinding the compound withextenders, for example solvents, solid carriers and, optionally, surfaceactive compounds (surfactants).

The application methods for the compositions, that is the methods ofcontrolling pests of the abovementioned type, such as spraying,atomizing, dusting, brushing on, dressing, scattering or pouring—whichare to be selected to suit the intended aims of the prevailingcircumstances—and the use of the compositions for controlling pests ofthe abovementioned type are other subjects of the invention. Typicalrates of concentration are between 0.1 and 1000 ppm, preferably between0.1 and 500 ppm, of active ingredient. The rate of application perhectare is preferably 1 g to 2000 g of active ingredient per hectare,more preferably 10 to 1000 g/ha, most preferably 10 to 600 g/ha. Whenused as seed drenching agent, convenient dosages are from 10 mg to 1 gof active substance per kg of seeds.

When the combinations of the present invention are used for treatingseed, rates of 0.001 to 50 g of a compound of formula (I) per kg ofseed, preferably from 0.01 to 10 g per kg of seed are generallysufficient.

Suitably, a composition comprising a compound of formula (I) accordingto the present invention is applied either preventative, meaning priorto disease development or curative, meaning after disease development.

The compositions of the invention may be employed in any conventionalform, for example in the form of a twin pack, a powder for dry seedtreatment (DS), an emulsion for seed treatment (ES), a flowableconcentrate for seed treatment (FS), a solution for seed treatment (LS),a water dispersible powder for seed treatment (WS), a capsule suspensionfor seed treatment (CF), a gel for seed treatment (GF), an emulsionconcentrate (EC), a suspension concentrate (SC), a suspo-emulsion (SE),a capsule suspension (CS), a water dispersible granule (WG), anemulsifiable granule (EG), an emulsion, water in oil (EO), an emulsion,oil in water (EW), a micro-emulsion (ME), an oil dispersion (OD), an oilmiscible flowable (OF), an oil miscible liquid (OL), a solubleconcentrate (SL), an ultra-low volume suspension (SU), an ultra-lowvolume liquid (UL), a technical concentrate (TK), a dispersibleconcentrate (DC), a wettable powder (WP) or any technically feasibleformulation in combination with agriculturally acceptable adjuvants.

Such compositions may be produced in conventional manner, e.g. by mixingthe active ingredients with appropriate formulation inerts (diluents,solvents, fillers and optionally other formulating ingredients such assurfactants, biocides, anti-freeze, stickers, thickeners and compoundsthat provide adjuvancy effects). Also conventional slow releaseformulations may be employed where long lasting efficacy is intended.Particularly formulations to be applied in spraying forms, such as waterdispersible concentrates (e.g. EC, SC, DC, OD, SE, EW, EO and the like),wettable powders and granules, may contain surfactants such as wettingand dispersing agents and other compounds that provide adjuvancyeffects, e.g. the ondensation product of formaldehyde with naphthalenesulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkylsulphate, and ethoxylated alkylphenol and an ethoxylated fatty alcohol.

A seed dressing formulation is applied in a manner known per se to theseeds employing the combination of the invention and a diluent insuitable seed dressing formulation form, e.g. as an aqueous suspensionor in a dry powder form having good adherence to the seeds. Such seeddressing formulations are known in the art. Seed dressing formulationsmay contain the single active ingredients or the combination of activeingredients in encapsulated form, e.g. as slow release capsules ormicrocapsules.

In general, the formulations include from 0.01 to 90% by weight ofactive agent, from 0 to 20% agriculturally acceptable surfactant and 10to 99.99% solid or liquid formulation inerts and adjuvant(s), the activeagent consisting of at least the compound of formula (I) together withcomponent (B) and (C), and optionally other active agents, particularlymicrobiocides or conservatives or the like. Concentrated forms ofcompositions generally contain in between about 2 and 80%, preferablybetween about 5 and 70% by weight of active agent. Application forms offormulation may for example contain from 0.01 to 20% by weight,preferably from 0.01 to 5% by weight of active agent. Whereas commercialproducts will preferably be formulated as concentrates, the end userwill normally employ diluted formulations.

Whereas it is preferred to formulate commercial products asconcentrates, the end user will normally use dilute formulations.

EXAMPLES

The Examples which follow serve to illustrate the invention. Certaincompounds of the invention can be distinguished from known compounds byvirtue of greater efficacy at low application rates, which can beverified by the person skilled in the art using the experimentalprocedures outlined in the Examples, using lower application rates ifnecessary, for example 50 ppm, 12.5 ppm, 6 ppm, 3 ppm, 1.5 ppm, 0.8 ppmor 0.2 ppm.

Throughout this description, temperatures are given in degrees Celsiusand “m.p.” means melting point. LC/MS means Liquid Chromatography MassSpectroscopy.

Formulation Examples

Wettable powders a) b) c) active ingredient [compound of formula (I)]25%  50% 75% sodium lignosulfonate 5%  5% — sodium lauryl sulfate 3% — 5% sodium diisobutylnaphthalenesulfonate —  6% 10% phenol polyethyleneglycol ether —  2% — (7-8 mol of ethylene oxide) highly dispersedsilicic acid 5% 10% 10% Kaolin 62%  27% —The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording wettablepowders that can be diluted with water to give suspensions of thedesired concentration.

Powders for dry seed treatment a) b) c) active ingredient [compound offormula (I)] 25% 50% 75% light mineral oil  5%  5%  5% highly dispersedsilicic acid  5%  5% — Kaolin 65% 40% — Talcum — 20 The active ingredient is thoroughly mixed with the adjuvants and themixture is thoroughly ground in a suitable mill, affording powders thatcan be used directly for seed treatment.

Emulsifiable concentrate active ingredient [compound of formula (I)] 10%octylphenol polyethylene glycol ether  3% (4-5 mol of ethylene oxide)calcium dodecylbenzenesulfonate  3% castor oil polyglycol ether (35 molof ethylene oxide)  4% Cyclohexanone 30% xylene mixture 50%Emulsions of any required dilution, which can be used in plantprotection, can be obtained from this concentrate by dilution withwater.

Dusts a) b) c) Active ingredient [compound of formula (I)]  5%  6%  4%talcum 95% — — Kaolin — 94% — mineral filler — — 96%Ready-for-use dusts are obtained by mixing the active ingredient withthe carrier and grinding the mixture in a suitable mill. Such powderscan also be used for dry dressings for seed.

Extruder granules Active ingredient [compound of formula (I)] 15% sodiumlignosulfonate  2% carboxymethylcellulose  1% Kaolin 82%The active ingredient is mixed and ground with the adjuvants, and themixture is moistened with water. The mixture is extruded and then driedin a stream of air.

Coated granules Active ingredient [compound of formula (I)] 8%polyethylene glycol (mol. wt. 200) 3% Kaolin 89% The finely ground active ingredient is uniformly applied, in a mixer, tothe kaolin moistened with polyethylene glycol. Non-dusty coated granulesare obtained in this manner.

Suspension concentrate active ingredient [compound of formula (I)] 40%propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol ofethylene oxide)  6% Sodium lignosulfonate 10% carboxymethylcellulose  1%silicone oil (in the form of a 75% emulsion in water)  1% Water 32%The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Flowable concentrate for seed treatment active ingredient [compound offormula (I)] 40%  propylene glycol 5% copolymer butanol PO/EO 2%tristyrenephenole with 10-20 moles EO 2% 1,2-benzisothiazolin-3-one (inthe form of a 20% solution 0.5%  in water) monoazo-pigment calcium salt5% Silicone oil (in the form of a 75% emulsion in water) 0.2%  Water45.3%  The finely ground active ingredient is intimately mixed with theadjuvants, giving a suspension concentrate from which suspensions of anydesired dilution can be obtained by dilution with water. Using suchdilutions, living plants as well as plant propagation material can betreated and protected against infestation by microorganisms, byspraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula (I) are mixed with2 parts of an aromatic solvent and 7 parts of toluenediisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). Thismixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol,0.05 parts of a defoamer and 51.6 parts of water until the desiredparticle size is achieved. To this emulsion a mixture of 2.8 parts1,6-diaminohexane in 5.3 parts of water is added. The mixture isagitated until the polymerization reaction is completed.The obtained capsule suspension is stabilized by adding 0.25 parts of athickener and 3 parts of a dispersing agent. The capsule suspensionformulation contains 28% of the active ingredients. The medium capsulediameter is 8-15 microns.The resulting formulation is applied to seeds as an aqueous suspensionin an apparatus suitable for that purpose.

Preparation examples Example 1: this Example Illustrates the PreparationofN-ethyl-N′-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine(Compound 1.22) Preparation ofN-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine

N′-(4-bromo-5-methoxy-2-methyl-phenyl)-N-ethyl-N-methyl-formamidine (6.0g, 21.04 mmol) was dissolved in tetrahydrofuran (84 mL) and cooled to−78° C. A 2N n-butyl lithium solution in cyclohexane (18.9 mL, 37.87mmol) was added dropwise. The resulting yellow solution was stirred for1 h at −78° C. Ethyl 2,2,2-trifluoroacetate (8.97 g, 63.128 mmol) neatwas added dropwise. At the end of the addition the cooling bath wasremoved and the reaction was warmed to 0-5° C. and then quenched with asaturated ammonium chloride solution. The mixture was extracted withethyl acetate. The organic layer was washed with brine, dried oversodium sulfate, filtered and concentrated under reduce pressure.

The residue was purified by chromatography on silica gel, using ethylacetate/dichloromethane as eluent system, to deliverN-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine(5.1 g, 16.89 mmol).

Major isomer: ¹H-NMR (400 MHz, CDCl₃): δ=1.27 (t, 3H), 2.22 (s, 3H),3.08 (s, 3H), 3.41 (d, 2H), 3.90 (s, 3H), 6.36 (br. s, 1H), 7.56 (br. s,2H)

Minor isomer: ¹H-NMR (400 MHz, CDCl₃): δ=1.27 (t, 3H), 2.22 (s, 3H),3.08 (s, 3H), 3.62 (d, 2H), 3.90 (s, 3H), 6.36 (br. s, 1H), 7.50 (s,1H), 7.56 (br. s, 1H) Ratio E/Z:3:5

Preparation ofN-ethyl-N′-[4-[1-hydroxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine

To a solution ofN-ethyl-N′-[5-methoxy-2-methyl-4-(2,2,2-trifluoroacetyl)phenyl]-N-methyl-formamidine(2.00 g, 6.29 mmol) in tetrahydrofuran (7 mL) was addedbromo(vinyl)magnesium (7.23 mL, 7.23 mmol) was added dropwise at −5° C.and the reaction mixture was stirred at 0° C. for 45 min. The reactionmixture was filtrated and poured on cooled water (15 mL), then aqueousammonium chloride solution was added until disappearance of theprecipitate and the mixture was extracted with ethyl acetate (3×20 mL).The combined organic layers were washed with brine, dried over sodiumsulfate, filtered and concentrated under vacuum to affordN-ethyl-N′-[4-[1-hydroxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine(2.20 g, 5.99 mmol). The material was used as crude for the next step.

¹H-NMR (400 MHz, CDCl₃): δ=7.46 (1H, m), 7.07 (1H, s), 6.42 (2H, m),6.31 (1H, s), 5.77 (1H, d), 5.52 (1H, d), 3.93 (3H, br s), 3.36 (2H, m),3.03 (3H, s), 2.21 (3H, s), 1.24 (3H, t)

Preparation ofN′-[4-[1-allyloxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine

To a solution ofN-ethyl-N′-[4-[1-hydroxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-methyl-formamidine(2.25 g, 6.13 mmol) in N,N-dimethylformamide (24.5 mL) was added sodiumhydride (0.258 g, 6.74 mmol) portionwise. The reaction mixture wasstirred at room temperature for 30 min. Then, allyl bromide (0.536 mL,6.13 mmol) was added dropwise and the reaction mixture was stirred atroom temperature for overnight. The reaction mixture was quenched withslow addition of saturated ammonium chloride solution (20 mL) and thenextracted with ethyl acetate (3×15 mL). The combined organic layers werewashed with water (2×100 mL), brine, dried over sodium sulfate, filteredand concentrated under vacuum. The crude material was purified bychromatography on silica gel using (ethyl acetate/cyclohexane as eluentsystem, to deliverN′-[4-[1-allyloxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine(1.99 g, 5.3 mmol).

¹H-NMR (400 MHz, DMSO): δ=1.14 (t, 3H), 2.12 (s, 3H), 2.86-3.08 (m, 3H),3.44 (m, 2H), 3.70 (s, 3H), 3.85 (d, 2H), 5.17 (dd, 1H), 5.33 (m, 2H),5.49 (d, 1H), 5.93 (1H, m), 6.32 (dd, 1H), 6.52 (s, 1H), 7.17 (s, 1H),7.59-7.86 (m, 1H)

Preparation ofN-ethyl-N′-[5-methoxy-2-methyl-4-[5-(trifluoromethyl)-2H-furan-5-yl]phenyl]-N-methyl-formamidine

A solution ofN′-[4-[1-allyloxy-1-(trifluoromethyl)allyl]-5-methoxy-2-methyl-phenyl]-N-ethyl-N-methyl-formamidine(1.00 g, 2.7 mmol) in dichloromethane (54.0 mL) was degassed with argonbefore benzylidene- bis(tricyclohexylphosphine)dichlororuthenium (0.113g, 0.135 mmol) was added. The reaction mixture was stirred at roomtemperature overnight. The reaction mixture was concentrated undervacuum then the residue was taken-up in water (60 mL) and acidified withHCl 2M. The mixture was extracted with diethyl ether (2×20 mL) then theaqueous layer was basified with aqueous sodium bicarbonate solution(until pH 10). The solution was extracted with dichloromethane (3×20 mL)and the combined organic layers were washed with brine, dried oversodium sulfate, filtered and concentrated under vacuum. The crudematerial was purified by chromatography on silica gel using (ethylacetate/cyclohexane as eluent system to deliverN-ethyl-N′-[5-methoxy-2-methyl-4-[5-(trifluoromethyl)-2H-furan-5-yl]phenyl]-N-methyl-formamidine(0.90 g, 2.6 mmol).

¹H-NMR (400 MHz, DMSO): δ=8.22-8.62 (1H, m), 7.49 (1H, s), 7.14 (2H, m),6.26-6.69 (2H, m), 4.59-4.92 (2H, m), 3.86 (3H, s), 3.57-3.78 (2H, m),3.28-3.36 (3H, m), 2.30 (3H, m), 1.28 (3H, t).

Preparation ofN-ethyl-N′-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine(Compound 1.22)

A solution ofN-ethyl-N′-[5-methoxy-2-methyl-4-[5-(trifluoromethyl)-2H-furan-5-yl]phenyl]-N-methyl-formamidine(200 mg, 0.58 mmol) in ethanol (6 mL) was degassed with argon andpalladium on charcoal (0.01869 g, cat.) was added. The reaction mixturewas stirred under hydrogen atmosphere at room temperature for 4 h. Thereaction mixture was filtrated through celite and the filtrate wasconcentrated under vacuum. The solid was taken-up in water (20 mL) andacidified with HCl until reaching pH 1. The mixture was extracted withdiethyl ether (10 mL) and the aqueous layer was basified with NaHCO3.The mixture was extracted with dichloromethane (3×10mL) and the combinedorganic layers were washed with brine, dried over sodium sulfate,filtered and concentrated under vacuum to affordN-ethyl-N′-[5-methoxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine(Compound 1.22, 98 mg, 0.29 mmol).

¹H-NMR (400 MHz, DMSO): δ=7.72 (1H, s), 7.27 (1H, s), 6.48 (1H, s), 3.77(4H, s), 3.33 (2H, m), 2.99 (3H, br s), 2.64 (1H, ddd), 2.38 (1H, dt),2.10 (3H, s), 2.00 (2H, m), 1.14 (3H, m).

Table E: Physical (LC/MS) Data of Certain Compounds of Formula (I) LC/MS(Liquid Chromatography Mass Spectrometry) Method Used

(ACQUITY UPLC from Waters, Phenomenex Gemini C18, 3 μm particle size,110 Angström, 30×3 mm column, 1.7 mL/min., 60° C., H₂O+0.05% HCOOH(95%)/CH₃CN/MeOH 4:1+0.04% HCOOH (5%)—2 min.—CH₃CN/MeOH 4:1+0.04% HCOOH(5%)−0.8 min., ACQUITY SQD Mass Spectrometer from Waters, ionizationmethod: electrospray (ESI), Polarity: positive ions, Capillary (kV)3.00, Cone (V) 20.00, Extractor (V) 3.00, Source Temperature (° C.) 150,Desolvation Temperature (° C.) 400, Cone Gas Flow (L/Hr) 60, DesolvationGas Flow (L/Hr) 700)).

Compound No. Name Structure LC/MS 1.21 N-ethyl-N′-[5-methoxy-2-methyl-4-[2- (trifluoromethyl)oxetan-2- yl]phenyl]-N-methyl- formamidine

Rt = 0.64 min; MS: m/z = 331 (M + 1) 1.22 N-ethyl-N′-[5-methoxy-2-methyl-4-[2- (trifluoromethyl)tetrahydro furan-2-yl]phenyl]-N-methyl-formamidine

Rt = 0.65 min; MS: m/z = 345 (M + 1)

Biological Examples Blumeria graminis f. sp. tritici (Erysiphe graminisf. sp. tritici)/Wheat/Leaf Disc Preventative (Powdery Mildew on Wheat)

Wheat leaf segments cv. Kanzler were placed on agar in a multiwell plate(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks were inoculated by shaking powdery mildewinfected plants above the test plates 1 day after application. Theinoculated leaf disks were incubated at 20° C. and 60% rh under a lightregime of 24 h darkness followed by 12 h light/12 h darkness in aclimate chamber and the activity of a compound was assessed as percentdisease control compared to untreated when an appropriate level ofdisease damage appears on untreated check leaf segments (6-8 days afterapplication).

The following compounds gave gave at least 80% disease control at 200ppm in this test when compared to untreated control leaf disks under thesame conditions, which show extensive disease development:

1.21 and 1.22

Phakopsora pachyrhizi/Soybean/Leaf Disk Preventative (Soybean Rust)

Four-week old soybean plants are sprayed in a spray chamber with theformulated test compound diluted in water. Leaf disks are cut fromtreated plants and placed on agar into 24-well plates one day afterapplication. Leaf disks are inoculated by spraying them with a sporesuspension on their lower leaf surface. After an incubation period in aclimate cabinet of 24-36 hours in darkness at 20° C. and 75% rh, theleaf disks are then kept at 20° C. with 12 h light/day and 75% rh. Thepercentage leaf disk area covered by disease is assessed when anappropriate level of disease appears on untreated check plants (12-14days after application).

The following compounds gave gave at least 80% disease control at 200ppm in this test when compared to untreated control leaf disks under thesame conditions, which show extensive disease development:

1.21 and 1.22

Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Preventative (BrownRust)

Wheat leaf segments cv. Kanzler were placed on agar in multiwell plates(24-well format) and sprayed with the formulated test compound dilutedin water. The leaf disks were inoculated with a spore suspension of thefungus 1 day after application. The inoculated leaf segments wereincubated at 19° C. and 75% rh under a light regime of 12 h light/12 hdarkness in a climate cabinet and the activity of a compound wasassessed as percent disease control compared to untreated when anappropriate level of disease damage appears in untreated check leafsegments (7-9 days after application).

The following compounds gave gave at least 80% disease control at 200ppm in this test when compared to untreated control leaf disks under thesame conditions, which show extensive disease development:

1.21 and 1.22

Puccinia recondita f. sp. tritici/Wheat/Leaf Disc Curative (Brown rust)

Wheat leaf segments cv. Kanzler are placed on agar in multiwell plates(24-well format). The leaf segments are inoculated with a sporesuspension of the fungus. Plates were stored in darkness at 19° C. and75% rh. The formulated test compound diluted in water was applied 1 dayafter inoculation. The leaf segments were incubated at 19° C. and 75% rhunder a light regime of 12 h light/12 h darkness in a climate cabinetand the activity of a compound was assessed as percent disease controlcompared to untreated when an appropriate level of disease damageappears in untreated check leaf segments (6-8 days after application).

The following compounds gave gave at least 80% disease control at 200ppm in this test when compared to untreated control leaf disks under thesame conditions, which show extensive disease development:

1.21 and 1.22

What is claimed is:
 1. A compound of formula (I)

wherein R¹ and R² are each independently selected from C₁-C₄alkyl andC₃-C₈cycloalkyl; or R¹ and R² together with the nitrogen atom to whichthey are attached form a three- to six-membered saturated cyclic group;R³ is hydrogen, halogen or C₁-C₄ alkyl; R⁴ and R⁵ are each independentlyselected from hydrogen and C₁-C₄ alkyl; or R⁴ and R⁵ together with thecarbon atom to which they are attached form a carbonyl group (C═O); X isO, S or NCH₃; n is O or 1; or a salt, metal complex, stereoisomer orN-oxide thereof.
 2. A compound according to claim 1 wherein R¹ and R²are each independently C₁-C₄ alkyl.
 3. A compound according to claim 1wherein R³ is halogen or C₁-C₃ alkyl.
 4. A compound according to claim 1wherein R⁴ and R⁵ are each independently selected from hydrogen andmethyl, or R⁴ and R⁵ together with the carbon atom to which they areattached form a carbonyl group.
 5. A compound according to claim 1wherein R¹ and R² are each independently selected from methyl, ethyl andisopropyl.
 6. A compound according to claim 1 wherein R³ is fluoro,chloro or methyl.
 7. A compound according to claim 1 wherein R⁴ and R⁵are both hydrogen, or R⁴ and R⁵ together with the carbon atom to whichthey are attached form a carbonyl group.
 8. A compound according toclaim 1 wherein R¹ is methyl, ethyl or isopropyl and R² is methyl orethyl.
 9. A compound according to claim 1 wherein R³ is chloro or methyland R⁴ and R⁵ are both hydrogen.
 10. A compound according to claim 1wherein R¹ and R² are each independently selected from methyl, ethyl andisopropyl; R³ is fluoro, chloro or methyl; R⁴ and R⁵ are both hydrogen,or R⁴ and R⁵ together with the carbon atom to which they are attachedform a carbonyl group; X is O, S or NCH₃; n is O or 1; or a salt, metalcomplex, stereoisomer or N-oxide thereof.
 11. A compound according toclaim 1 wherein the compound is selected from:

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine;

N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-isopropyl-N-methyl-formamidine;

N′-[2-chloro-5-hydroxy-4-[2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-ethyl-N-methyl-formamidine;

N-ethyl-N′-[5-hydroxy-2-methyl-4-[4-oxo-2-(trifluoromethyl)tetrahydrofuran-2-yl]phenyl]-N-methyl-formamidine;

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)tetrahydrothiophen-2-yl]phenyl]-N-methyl-formamidine;or

N-ethyl-N′-[5-hydroxy-2-methyl-4-[2-(trifluoromethyl)oxetan-2-yl]phenyl]-N-methyl-formamidine;or a salt, metal complex, stereoisomer or N-oxide thereof.
 12. Acompound according to claim 1 wherein X is O or S.
 13. A compositioncomprising a fungicidally effective amount of a compound of formula (I)as defined in claim
 1. 14. A composition according to claim 13, whereinthe composition further comprises at least one additional activeingredient and/or a diluent.
 15. A method of combating, preventing orcontrolling phytopathogenic fungi which comprises applying tophytopathogenic fungi, to the locus of phytopathogenic fungi, or to aplant susceptible to attack by phytopathogenic fungi, or to propagationmaterial thereof, a fungicidally effective amount of a compound offormula (I) as defined in claim
 1. 16. A method of combating, preventingor controlling phytopathogenic fungi which comprises applying tophytopathogenic fungi, to the locus of phytopathogenic fungi, or to aplant susceptible to attack by phytopathogenic fungi, or to propagationmaterial thereof, a composition comprising a fungicidally effectiveamount of a compound of formula (I) as defined in claim 1.